CN101872837B - Resistive layer, resistive storage having same and process for preparing same - Google Patents

Resistive layer, resistive storage having same and process for preparing same Download PDF

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CN101872837B
CN101872837B CN2009100828904A CN200910082890A CN101872837B CN 101872837 B CN101872837 B CN 101872837B CN 2009100828904 A CN2009100828904 A CN 2009100828904A CN 200910082890 A CN200910082890 A CN 200910082890A CN 101872837 B CN101872837 B CN 101872837B
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layer
resistance
storing device
preparation technology
variable storing
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CN101872837A (en
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康晋锋
高滨
余诗孟
刘力锋
孙兵
刘晓彦
韩汝琦
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Peking University
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Peking University
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Abstract

The invention relates to the technical field of microelectronic semiconductors and discloses a resistive layer, a resistive storage having the same, and a process for preparing the same. In the invention, a process method of forming an alloy layer by depositing three layers of metal thin films on a bottom electrode of the resistive storage continuously and then forming the resistive layer is used to realize the effective control over the generation of medium- and thin-wire conductive channels in the resistive layer to improve the consistency of the resistive storage. The process is compatible with the conventional semiconductor production process and is simple and low in production cost.

Description

A kind of change resistance layer with have the resistance-variable storing device and a preparation technology of this change resistance layer
Technical field
The present invention relates to the semiconductor microelectronics technical field, particularly relate to and a kind ofly improve the change resistance layer of the metal oxide based resistance-type memory performance of transition and have the resistance-variable storing device preparation technology and the structure thereof of this change resistance layer.
Background technology
At present, the development of semi-conductor industry is just promoting the continuous progress of memory technology.Wherein utilize the novel non-volatility memorizer of resistance variations,, be easy to advantages such as integrated, become the strong competitor of semiconductor memory of future generation owing to its high storage density, high-speed, low-power consumption.This resistance-variable storing device generally has M-I-M (Metal-Insulator-Metal; Metal-insulator-metal type) structure; Promptly between the double layer of metal electrode, add one deck and have the dielectric thin-film material that resistance becomes characteristic; Its operation principle is to utilize applied voltage to vary in size or the polarity of voltage difference, and the control resistance becomes the resistance value of material to be changed between high low resistance state, to realize writing and wiping of data.It all is metal-oxide film that at present common resistance becomes material many, hafnium oxide (HfO2) for example, titanium oxide (TiO2), zirconia (ZrO2), nickel oxide (NiO), zinc oxide (ZnO), tungsten oxide (W 2O 5) etc.
Research shows; Why above-mentioned resistance-variable storing device can be changed between different resistance states each other; Mainly with relevant at the inner filament conductive channel that forms of dielectric thin-film material; The break-make of these filament conductive channels has determined the memory cell of resistance-variable storing device to be in high-impedance state or low resistance state, and therefore effectively the formation of control filament conductive channel is the key that improves memory performance.Because it is very complicated that at present common resistance becomes the character of the metal oxide materials system of using in the material; Utilize that the formation of filament conductive channel has very big randomness in the medium of oxides film of existing process method and technical scheme preparation; Can not effectively control the formation of filament conductive channel; Make that thus the consistency of prepared resistance-variable storing device is relatively poor, be difficult to satisfy the demand of technical application.
Summary of the invention
The purpose of this invention is to provide a kind of formation that can effectively control filament conductive channel in the resistance change material oxide dielectric film, thereby improve the conforming technical scheme of metal oxide based resistance-variable storing device memory cell.
For achieving the above object, technical scheme of the present invention provides a kind of change resistance layer and has the resistance-variable storing device and the preparation technology of this change resistance layer ...
Technique scheme has following advantage: form alloy-layer to be prepared into change resistance layer through consecutive deposition three-layer metal film on hearth electrode; Utilize this change resistance layer to realize effective control that the filament conductive channel is produced; The present invention can be compatible mutually with traditional production process of semiconductor; Technology is simple, and production cost is low.
Description of drawings
Fig. 1 is preparation technology's flow chart of the resistance-variable storing device of the embodiment of the invention;
Fig. 2 is the structural representation of the resistance-variable storing device of the embodiment of the invention;
Fig. 3 is the sketch map that utilizes TEM that the cross section of the resistance-variable storing device of the embodiment of the invention is analyzed;
Fig. 4 utilizes EDX the cross section of the resistance-variable storing device of the embodiment of the invention to be carried out the sketch map of constituent analysis;
Fig. 5 is the comparison sketch map that the resistance-variable storing device of resistance-variable storing device and the conventional oxidation hafnium structure of the embodiment of the invention forms voltage;
Fig. 6 is the comparison sketch map of resistance-variable storing device shift voltage of resistance-variable storing device and the conventional oxidation hafnium structure of the embodiment of the invention;
Fig. 7 is the comparison sketch map of resistance-variable storing device low-resistance resistance of resistance-variable storing device and the conventional oxidation hafnium structure of the embodiment of the invention;
Fig. 8 is the comparison sketch map of resistance-variable storing device high resistant resistance of resistance-variable storing device and the conventional oxidation hafnium structure of the embodiment of the invention.
Embodiment
Below in conjunction with accompanying drawing and embodiment, specific embodiments of the invention describes in further detail.Following examples are used to explain the present invention, but are not used for limiting scope of the present invention.
As shown in Figure 1, be preparation technology's flow chart of the resistance-variable storing device of the embodiment of the invention.The step of preparation process of resistance-variable storing device is:
Step 101 is thermal oxidation layer of silicon dioxide (SiO on the substrate of silicon chip at material 2) utilize physical vapor deposition again mode deposit layer of metal titanium (Ti) as resilient coating, utilize the mode deposit hearth electrode of physical vapor deposition then, hearth electrode uses resistance-variable storing device electrode material commonly used, selects Pt in the present embodiment.Its thickness is greater than 50 nanometers.
Step 102, the mode of on hearth electrode, utilizing physical vapor deposition is deposit three-layer metal film successively, and wherein, the double layer of metal film is Al up and down, and levels Al thickness is all selected 5 nanometers; The metallic intermediate layer film is the metallic film of the routine of preparation change resistance layer in the prior art.Select Hf in the present embodiment, the thickness of the Hf of institute's deposit is 20 nanometers.
Step 103 with the annealing 20 minutes in nitrogen or other inert gas atmosphere, in about 600 ℃ the temperature range of above-mentioned three-layer metal film, makes bilevel Al in the Hf in intermediate layer, spread and dissolving formation alloy firm each other.Said temperature and annealing time are inversely proportional to, promptly time of then needing of temperature height short, the low time that then needs of temperature is long, reaches bilevel Al spread and mutual purpose of dissolving gets final product in the Hf in intermediate layer.
Step 104 will be through anneal oxidation in the atmosphere of alloy firm at oxygen after the step S2 annealing, in about 600 ℃ the temperature range 20 minutes, makes Hf, Al oxidation become the oxide that Al and Hf mix, and forms change resistance layer.Said temperature and annealing time are inversely proportional to, promptly time of then needing of temperature height short, the low time that then needs of temperature is long, reaches Hf, the oxidized purpose of Al are got final product.
Step 105 is utilized the mode deposit top electrode of physical vapor deposition on above-mentioned change resistance layer.Top electrode uses resistance-variable storing device electrode material commonly used, selects TiN here.Its thickness is greater than 50 nanometers.
Step 106 utilizes photoetching technique said hearth electrode, change resistance layer and top electrode to be isolated into after the memory cell of separation, said hearth electrode, change resistance layer, and top electrode and substrate form said resistance-variable storing device.
Step 107 goes between and subsequent technique such as passivation to the resistance-variable storing device that after above-mentioned processing, forms.
Pt in the above-mentioned steps can use other resistance-variable storing device electrode material commonly used; Replace like gold (Au), titanium nitride (TiN), tungsten (W); Al can use lanthanum (La) to replace; The metallic intermediate layer film can use zirconium (Zr) to replace, and top electrode can replace like platinum (Pt), tungsten (W) with resistance-variable storing device electrode material commonly used.
Need to prove that the preparation technology of the change resistance layer of the embodiment of the invention has been included among the preparation technology of resistance-variable storing device, be step 102 to the step 104 of above-mentioned steps.
The resistance-variable storing device that forms through above-mentioned preparation technology comprises substrate and is positioned at the M-I-M device architecture on the substrate; Its structural representation is as shown in Figure 2; Comprise four-layer structure; Be followed successively by substrate 201, hearth electrode 202, resistance pole-changing 203 and top electrode 204 from down to up, resistance pole-changing 203 comprises metallic intermediate layer sull HfO 2Layer and two-layer Al layer metallic film up and down.Above-mentioned four-layer structure all is connected with the mode of physical vapor deposition.Need to prove that the structure of the change resistance layer of the embodiment of the invention has been included in the structure of resistance-variable storing device, specifically sees Fig. 2.
When resistance-variable storing device of the present invention is worked, between top electrode and hearth electrode, apply a bigger formation voltage earlier,, make the M-I-M devices get into low resistance state like 5V.And then apply the pulse voltage of forward and negative sense respectively, like 2V, the M-I-M device is changed between high-impedance state and two resistance states of low resistance state; Use very little pulse voltage; Like 0.5V, read current value, to confirm which state the M-I-M device is in through memory cell.Above-mentioned pulse voltage can be replaced by continuous direct current scanning voltage.
Because the Al atom has very strong diffusivity; Be easy to be diffused into and form the alloy-layer that Hf mixes with Al among the Hf; Use TEM (Transmission ElectronMicroscope among Fig. 3 and Fig. 4 respectively; Transmission electron microscope) and EDX (Energy Dispersive X-RaySpectrometer, X ray energy dispersive spectrum) result that hearth electrode, change resistance layer and the top electrode of the resistance variohm of the embodiment of the invention are measured proved this point.As shown in Figure 3, be the TEM sectional view, show the thickness of above-mentioned hearth electrode, change resistance layer and top electrode, the brightest above zone is top electrode TiN, and the centre is a change resistance layer, and the darkest below zone is hearth electrode Pt.As shown in Figure 3, the origin of coordinates of " 1 " some corresponding diagram 4, red vertical line is represented the zone and the direction of EDX scanning, i.e. the axis of abscissas of corresponding right figure.Therefore presentation graphs 4 is from the scanning direction of top electrode to hearth electrode among the figure.Engineer's scale in " 20nm " and the corresponding red horizontal line similar map, the corresponding actual 20nm of the corresponding length of red horizontal line in the presentation graphs 3.As shown in Figure 4, the big or small corresponding respective element of ordinate value is in this regional concentration in the EDX spectral line, and as can be seen from the figure, in the zone less than 5nm, the content of Ti has accounted for the overwhelming majority, explains that this zone is TiN, shows that this zone is a top electrode; In the zone of＞10nm, the content of Hf obviously increases, and explains that this zone is HfO 2, show that this zone is a change resistance layer, but also very high at the content of this regional Al, explain that Al spreads, and dissolve each other with Hf.
And in utilizing the change resistance layer of prepared of the present invention, the filament conductive channel mainly forms near the Al atom in the change resistance layer, has so just realized the filament conductive channel is produced effectively control, thereby can effectively improve the consistency of resistance-variable storing device.The resistance that Fig. 5 to Fig. 8 shows the resistance-variable storing device that adopts prepared of the present invention and the conventional oxidation hafnium structure resistance-variable storing device of prior art for preparing becomes the characteristic comparison.To shown in Figure 8, wherein, μ representes mean value, V like Fig. 5 fExpression forms voltage, μ (V f) expression forms the mean value of voltage, σ representes standard deviation, σ (V f) expression forms the standard deviation of voltage, is that the quantitative statistics of the formation voltage among Fig. 5 is described; Vset representes setting voltage, μ (V Set) mean value of expression set voltage, σ (V Set) expression shift voltage standard deviation; R LRSExpression low resistance state resistance, R HRSExpression high-impedance state resistance, σ (R LRS)/μ (R LRS) standard deviation of expression low resistance state resistance and the ratio of the mean value of low resistance state resistance, σ (R HRS)/μ (R HRS) standard deviation of expression high-impedance state resistance and the ratio of the mean value of high-impedance state resistance.
Can find out directly that from the data of Fig. 5 to Fig. 8 the oxide that adopts Al and Hf to mix (is the Al:HfO among Fig. 5 to Fig. 8 2) resistance-variable storing device (being called for short the Hf-Al device) of forming change resistance layer compares with the resistance-variable storing device (being called for short pure Hf device) of pure relatively Hf composition change resistance layer; The discreteness of the former voltage, resistance has all reduced, i.e. the consistency that the resistance of resistance-variable storing device becomes characteristic has improved.Specifically, be example with Fig. 7, the low resistance state resistance of the corresponding Hf-Al device of black circle behind each the transformation, the corresponding pure Hf device low resistance state resistance of hollow side's point, ordinate representes that resistance accounts for the percentage of sum less than the quantity of the corresponding resistance of this abscissa.The resistance that can find out the Hf-Al device all concentrates on about 200 Europe, and pure Hf device resistance all has distribution from 200 Europe to 3000 Europe, explains that discreteness is very big.
Can find out by above embodiment; The embodiment of the invention forms change resistance layer through being employed in the consecutive deposition three-layer metal through preparation; The filament conductive channel is mainly formed near the Al atom in the change resistance layer; Realized the filament conductive channel is produced effectively control, thereby effectively improved the consistency of resistance-variable storing device.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from know-why of the present invention; Can also make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention.

Claims (11)

1. the preparation technology of a change resistance layer is characterized in that, comprises the steps:
S1, deposit three-layer metal film successively on hearth electrode, wherein, two-layer up and down is aluminium or lanthanum, the intermediate layer is hafnium or zirconium; Said two layers of thickness up and down is 3 nanometer to 7 nanometers, and said intermediate layer thickness is 10 nanometer to 30 nanometers;
S2 carries out annealing in process with said three-layer metal film in inert gas atmosphere, the double layer of metal film spreads in the metallic intermediate layer film and dissolves each other and forms alloy firm about making;
S3 will carry out annealing in process in the atmosphere of alloy firm at oxygen after the step S2 annealing, make the oxidized formation metal-oxide film of alloy firm, and formed metal-oxide film constitutes the change resistance layer of resistance-variable storing device.
2. the preparation technology of change resistance layer as claimed in claim 1 is characterized in that, the temperature of the annealing in process among said step S2 and the said step S3 is 500 ℃ to 800 ℃, carries out 5 to 30 minutes.
3. the preparation technology of change resistance layer as claimed in claim 1 is characterized in that, said two-layer up and down be aluminium, the intermediate layer is a hafnium.
4. the preparation technology of change resistance layer as claimed in claim 3 is characterized in that, said two layers of thickness up and down is 5 nanometers, and said intermediate layer thickness is 20 nanometers.
5. the preparation technology of change resistance layer as claimed in claim 4 is characterized in that, the annealing in process among said step S2 and the said step S3 was carried out under 600 ℃ temperature conditions 20 minutes.
6. the preparation technology of change resistance layer as claimed in claim 1 is characterized in that, the deposit mode among the said step S1 is a physical vapor deposition.
7. the change resistance layer of the preparation technology of an arbitrary described change resistance layer that utilizes claim 1 to 6 preparation.
8. the preparation technology of a resistance-variable storing device is characterized in that, said preparation technology comprises the steps:
A1, deposit hearth electrode on a substrate;
A2 makes change resistance layer through the preparation technology like arbitrary described change resistance layer of claim 1 to 6;
A3, deposit top electrode on said change resistance layer;
A4 utilizes photoetching technique said hearth electrode, change resistance layer and top electrode to be isolated into after the memory cell of separation, said hearth electrode, change resistance layer, and top electrode and substrate form said resistance-variable storing device.
9. the preparation technology of resistance-variable storing device as claimed in claim 8 is characterized in that, after said steps A 4, also comprises the said resistance-variable storing device step with passivation that goes between.
10. the resistance-variable storing device of the preparation technology's preparation that utilizes the described resistance-variable storing device of claim 8.
11. resistance-variable storing device as claimed in claim 10 is characterized in that, said resistance-variable storing device is gone between and passivation.
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CN102487122A (en) * 2010-12-06 2012-06-06 中国科学院微电子研究所 Non-volatile resistance transformation memory and preparation method thereof
CN102623046B (en) 2011-01-28 2014-09-17 北京大学 Resistance changing device for realizing multinary addition calculation, and multinary addition calculation method
CN102157692B (en) * 2011-03-22 2012-08-22 复旦大学 Organic resistive random access memory (RRAM) with peak shaped bottom electrode and manufacture method thereof
CN111146341A (en) * 2020-01-02 2020-05-12 集美大学 Preparation method of resistive random access memory with space limitation effect
CN111564555B (en) * 2020-05-20 2022-04-12 浙江大学 Resistive random access memory for improving working stability and memory window and preparation method thereof

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CN101212019A (en) * 2006-12-26 2008-07-02 北京大学 Resistance random access memory unit and method for producing the same

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CN101212019A (en) * 2006-12-26 2008-07-02 北京大学 Resistance random access memory unit and method for producing the same

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